CN117285157A - Denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, and preparation method and application thereof - Google Patents

Denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, and preparation method and application thereof Download PDF

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Publication number
CN117285157A
CN117285157A CN202311309610.5A CN202311309610A CN117285157A CN 117285157 A CN117285157 A CN 117285157A CN 202311309610 A CN202311309610 A CN 202311309610A CN 117285157 A CN117285157 A CN 117285157A
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denitrifying bacteria
sewage
complexing agent
bacteria culture
nitrogen
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CN117285157B (en
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郑涛
刘立明
王胜男
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Beijing Tiancheng Zhonghe Technology Development Co ltd
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Beijing Tiancheng Zhonghe Technology Development Co ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/28Anaerobic digestion processes
    • C02F3/2806Anaerobic processes using solid supports for microorganisms
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20Bacteria; Culture media therefor
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12RINDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
    • C12R2001/00Microorganisms ; Processes using microorganisms
    • C12R2001/01Bacteria or Actinomycetales ; using bacteria or Actinomycetales
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

Abstract

The embodiment of the invention discloses a denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, a preparation method and application thereof. The denitrifying bacteria culture complexing agent comprises the following components in percentage by mass: 35% -60% of a sulfur source mixture, wherein the sulfur source mixture comprises a compound containing sulfur elements; 15% -60% of an iron source mixture, wherein the iron source mixture comprises a compound containing iron elements; 3% -8% of a stabilizer, wherein the stabilizer regulates the PH value of the denitrifying bacteria culture complexing agent; 3-10% of composite adhesive, wherein the composite adhesive is a carrier of denitrifying bacteria. The denitrifying bacteria culture complexing agent in the preparation method is prepared from a sulfur source mixture, an iron source mixture, a stabilizer and a composite adhesive. The denitrifying bacteria special culture medium mainly composed of iron and sulfur is used for directionally enriching sulfur autotrophic denitrifying bacteria and iron autotrophic denitrifying bacteria existing in nature, and a carbon source is not required to be added, so that total nitrogen can be removed efficiently, and secondary pollution is avoided.

Description

Denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, and preparation method and application thereof
Technical Field
The invention relates to the technical field of sewage treatment by denitrifying bacteria, in particular to a denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, a preparation method and application thereof.
Background
The nitrogen-containing pollutants in the water body are divided into organic nitrogen and inorganic nitrogen, wherein the inorganic nitrogen has 3 existing forms of ammonia nitrogen, nitrite nitrogen and nitrate nitrogen, and the organic nitrogen comprises amino acid, protein, urea and other organic compounds. When the nitrogen discharged into the water exceeds the self-cleaning capability of the water, the water can be eutrophicated, so that the drinking safety of surface water and underground water is affected, and the water can pose a threat to the health of human bodies and animals when serious.
The sewage biological treatment technology has become the main technology in the current sewage treatment field, is an economic and efficient water pollution control engineering means, and plays a vital role in improving the water environment quality and preventing the water pollution. Nitrogen in the wastewater is mainly removed through a nitrification and denitrification process. In the nitrification process, ammonia nitrogen is oxidized into nitrate or nitrite nitrogen by utilizing the action of nitrifying bacteria under aerobic conditions, which is a key nitrogen compound conversion process, and the step is helpful for converting harmful ammonia nitrogen into stable nitrate nitrogen, so that the negative influence on the water body environment is reduced. In the denitrification process, in the anoxic environment, denitrifying bacteria utilize organic matters as electron donors to reduce nitrate and nitrite into nitrogen, so that nitrogen compounds are completely removed from the water body, and the process is very critical for reducing the emission of nitrogen waste and improving the nitrogen load of the water body, especially in some areas with strict limits on nitrogen emission.
The denitrification requires an organic carbon source as an electron donor, nitrate nitrogen as an electron acceptor and finally converted into nitrogen, so that the aim of removing nitrogen in wastewater is fulfilled. The sewage treatment plant established in the early stage is only designed with a nitrification reaction tank, and has no denitrification function, and the newly built denitrification tank is transformed to cause the problems of capital investment and occupied land. After the total nitrogen removal effect of part of sewage treatment plants is improved, the COD of the effluent water can not reach the discharge standard, and the treatment of the residual sludge is always a difficult problem of the sewage treatment plants.
At present, the sewage discharge standard of China is stricter, the sewage discharge in most areas executes the first-level A discharge standard in the pollutant discharge standard of urban sewage plants (GB 18918-2002), and part of cities require the sewage discharge to execute the standards of surface water class V, class IV and even class III, thus higher requirements are provided for nitrogen removal. When sewage and wastewater with low carbon/nitrogen ratio are treated, the traditional heterotrophic denitrification is directly adopted, and a carbon source is required to be additionally added, so that secondary pollution is caused.
Disclosure of Invention
The invention aims to provide a denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, which is used for solving at least one technical problem, and the prepared denitrifying bacteria special culture medium mainly composed of iron and sulfur has the characteristics of specificity and high efficiency, provides needed nutrient substances for the denitrifying bacteria in a directional manner, enriches the sulfur autotrophic denitrifying bacteria and the iron autotrophic denitrifying bacteria existing in the nature in a directional manner, does not need to add additional carbon sources, can efficiently remove total nitrogen, saves energy and avoids secondary pollution.
The invention also aims to provide a preparation method of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, which can prepare the denitrifying bacteria special culture medium mainly composed of iron and sulfur, and has the advantages of simple and effective preparation method, low implementation cost and high efficiency in removing total nitrogen.
The invention also aims to provide an application of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, which can be used for carrying out targeted treatment on nitrogen substances in the sewage, so as to reduce the total nitrogen amount and realize standard discharge.
Embodiments of the present invention are implemented as follows:
a denitrifying bacteria culture complexing agent for degrading nitrogen in sewage comprises the following components in percentage by mass:
35% -60% of a sulfur source mixture, wherein the sulfur source mixture comprises a compound containing sulfur elements;
15% -60% of an iron source mixture, wherein the iron source mixture comprises a compound containing iron elements;
3% -8% of a stabilizer, wherein the stabilizer regulates the PH value of the denitrifying bacteria culture complexing agent;
3-10% of composite adhesive, wherein the composite adhesive is a carrier of denitrifying bacteria.
In a preferred embodiment of the present invention, the sulfur source mixture of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage includes sulfuric acid, sodium sulfide and sodium thiosulfate;
the sulfur source mixture comprises the following components in percentage by mass: sodium sulfide: sodium thiosulfate= (20-30): (15-25): (15-25).
The technical effects are as follows: ensures that different forms of sulfur compounds exist in the sulfur source mixture, provides diversity and is helpful for adapting to denitrification reactions under different environmental conditions. The mass ratio between different sulfur sources influences the speed and the efficiency of the denitrification reaction, and the efficiency of the denitrification reaction can be enhanced through the proper mass ratio, so that nitrate and nitrite can be reduced into nitrogen more effectively, and the performance of the denitrifying bacteria culture complexing agent can be regulated.
In a preferred embodiment of the present invention, the iron source mixture of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage includes manganese iron ore powder, ferrous hydroxide and magnetic iron oxide;
the iron source mixture comprises the following components in percentage by mass: ferrous hydroxide: magnetic iron oxide= (20-30): (0.5-3): (0.5-6).
The technical effects are as follows: ensures that iron compounds with different forms exist in the iron source mixture, provides diversity and is helpful for adapting to denitrification reactions under different environmental conditions. The mass ratio between different iron sources influences the speed and the efficiency of the denitrification reaction, and the efficiency of the denitrification reaction can be enhanced by accurately adjusting the proper mass ratio, so that nitrate and nitrite can be reduced into nitrogen more effectively, and the performance of the denitrifying bacteria culture complexing agent can be regulated.
In a preferred embodiment of the present invention, the stabilizer of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage includes calcium chloride and magnesium oxide;
the stabilizer comprises the following components in percentage by mass: magnesium oxide= (1-5): (0.3-3).
The technical effects are as follows: calcium chloride and magnesium oxide are relatively safe compounds, and small additions do not adversely affect the rancour wastewater treatment process. The pH value of the denitrifying bacteria culture complexing agent is adjusted through the synergistic effect of the calcium chloride and the magnesium oxide, so that the excessive fluctuation of the pH value is prevented, proper conditions are provided for the growth and the activity of bacteria, and the growth of the bacteria and the stability of the denitrification reaction are ensured. Meanwhile, calcium chloride and magnesium oxide are important components of cell synthesis and enzyme activity, and can be used as sources of calcium and magnesium through proper mass ratio to promote the growth and activity of denitrifying bacteria.
In a preferred embodiment of the present invention, the composite adhesive of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage includes phosphate, water-soluble natural resin and modifier;
the composite adhesive comprises the following components in percentage by mass: water-soluble natural resin: modifier= (20-35): (65-80): (2-10).
The technical effects are as follows: phosphate, water-soluble natural resin and modifier in the composite adhesive are taken as carriers of denitrifying bacteria to jointly form a basic structure of the composite adhesive, a proper growth and attachment surface is provided for bacteria, and meanwhile, the composite adhesive has adhesiveness and chemical stability through a proper proportion, so that the requirements of denitrifying bacteria culture are fully met.
In a preferred embodiment of the present invention, the modifier of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage includes silica nanoparticles, activated carbon, sodium dodecyl sulfate, polyvinyl alcohol and dimethyl ethylene diamine;
the mass ratio of each component in the modifier is that silicon oxide nano particles: activated carbon: sodium dodecyl sulfate: polyvinyl alcohol: dimethylethylenediamine= (1-5): (1-3): (1-3): (0.5-2): (0.5-1).
The technical effects are as follows: sodium dodecyl sulfate is used as a surfactant and can be used for improving the dispersibility of the composite adhesive; the polyvinyl alcohol is a modified polymer, so that the viscosity and the adhesiveness of the composite adhesive can be adjusted; the dimethyl ethylene diamine is used as a cross-linking agent, so that the stability and durability of the composite adhesive can be improved. By selecting proper modifier and improving the proportion, the adsorption performance and the surface activity of the composite adhesive are enhanced, and the attachment and the reaction of nitrifying bacteria on a substrate are promoted. The interaction of different components in the modifier improves the stability of the composite adhesive. The property and the characteristic of the composite adhesive are adjusted by precisely controlling the proportion, so that the culture requirement of specific denitrifying bacteria is met. So that the compound adhesive can be used as a carrier and can provide advantages in chemical properties such as reaction capability in the culture process of denitrifying bacteria.
The preparation method of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage comprises the following steps of:
s100, taking all the components according to mass percentages;
s200, adding the components into a container, mixing, grinding and uniformly stirring to obtain a mixture;
and S300, heating the mixture, calcining and forming at a high temperature of 160-180 ℃, and cooling at normal temperature to obtain a denitrifying bacteria culture complexing agent finished product.
The application of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage is characterized in that the denitrifying bacteria culture complexing agent is prepared from a sulfur source mixture, an iron source mixture, a stabilizer and a compound adhesive, wherein the components and the mass percentages of the components are as described above, and the application steps comprise:
s1000, inoculating sludge into the prepared denitrifying bacteria culture complexing agent to obtain bacterial nests;
s2000, cleaning the bacterial nest with distilled water, removing impurities, and centrifuging at 80rpm/S to obtain denitrifying bacteria filler;
s3000, sequentially filling cobbles, denitrifying bacteria fillers and sewage to be degraded from bottom to top in the sewage degradation reactor, introducing distilled water into the sewage degradation reactor through the adjustment of a water inlet valve, and controlling the aeration rate in the sewage degradation reactor through an oxygenation pump.
In a preferred embodiment of the present invention, in the application of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, the denitrifying bacteria in the bacterial nest include at least one of sulfur autotrophic denitrifying bacteria (thiobacillus denitrificans), pseudomonas pastoris (paracoccus pantotrophus), sulfamonas (sulfarimonas), iron autotrophic denitrifying bacteria (acidithiobacillus ferrooxidans) and iron sulfide (thiobacillus ferrooxidans).
The technical effects are as follows: through directional culture, the bacterial nest contains different types of denitrifying bacteria, such as sulfur autotrophic denitrifying bacteria, pseudomonas pastoris, sulfate monad, iron autotrophic denitrifying bacteria, sulfur ferric monad and the like, and the diversity is favorable for meeting nitrogen removal requirements under different water quality conditions, so that the adaptability and the stability of the treatment system are improved.
In a preferred embodiment of the present invention, in the application of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, a carbon source is added between the denitrifying bacteria filler and sewage to be degraded in the sewage degradation reactor, the carbon source includes shell powder, and the mass ratio of the denitrifying bacteria filler to the shell powder is that of the denitrifying bacteria filler: shell powder = 1:5, the preparation method of the shell powder comprises the following steps:
and (3) taking shells, cleaning the shells with distilled water, removing impurities, cleaning the shells with dilute hydrochloric acid, drying, and grinding to obtain shell powder.
The technical effects are as follows: the shell powder is added as a carbon source to provide additional organic carbon for denitrifying bacteria, which is helpful for promoting the growth and metabolism of bacteria. The mass ratio of denitrifying bacteria filler to shell powder is 1: and 5, adjusting the carbon-nitrogen ratio to ensure that the provided carbon source and nitrogen compounds in the sewage have proper proportions, thereby being beneficial to optimizing the denitrification reaction efficiency and improving the nitrogen removal performance.
The embodiment of the invention has the beneficial effects that:
the invention provides a denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, a preparation method and application thereof, which are used for degrading nitrogen pollutants in sewage, and a sulfur source and iron source mixture provides nutrient elements required by denitrifying bacteria, so that the growth and activity of the denitrifying bacteria are promoted, a stabilizer helps to maintain the stability of a culture environment, a composite adhesive serves as a carrier of microorganisms, and the stability of bacteria in culture is helped to be fixed and maintained.
The invention has the advantage of flexibility and adaptability. The ratio of the sulfur source and the iron source mixture in the complexing agent can be adjusted according to different water quality and treatment requirements so as to meet the degradation requirements under different environmental conditions. In addition, the invention is suitable for various sewage treatment scenes by adopting a plurality of different types of denitrifying bacteria, and improves the adaptability and the efficiency.
The invention has important functions of improving the water environmental quality and reducing nitrogen pollution. By adding the complexing agent into the sewage treatment reactor, nitrogen pollutants can be effectively removed, and the water resource and the ecological environment can be protected. In addition, the carbon source such as shell powder is added, so that the denitrification reaction efficiency can be further improved, and nitrogen compounds in sewage can be treated more effectively. In combination, the invention provides an economic and effective solution for the current sewage treatment field, and is expected to play a key role in water quality improvement and sewage treatment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a preparation method of a denitrifying bacteria culture complexing agent for degrading nitrogen in sewage;
FIG. 2 is a schematic diagram of the application steps of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage;
FIG. 3 is a schematic diagram of a reactor for degrading sewage in the application of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein can be arranged and designed in a wide variety of different configurations.
The invention provides a denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, which comprises the following components in percentage by mass: 35% -60% of a sulfur source mixture, wherein the sulfur source mixture comprises a compound containing sulfur elements; 15% -60% of an iron source mixture, wherein the iron source mixture comprises a compound containing iron elements; 3% -8% of a stabilizer, wherein the stabilizer regulates the PH value of the denitrifying bacteria culture complexing agent; 3-10% of composite adhesive, wherein the composite adhesive is a carrier of denitrifying bacteria.
In a preferred embodiment of the present invention, the sulfur source mixture of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage includes sulfuric acid, sodium sulfide and sodium thiosulfate; the sulfur source mixture comprises the following components in percentage by mass: sodium sulfide: sodium thiosulfate= (20-30): (15-25): (15-25). The technical effects are as follows: ensures that different forms of sulfur compounds exist in the sulfur source mixture, provides diversity and is helpful for adapting to denitrification reactions under different environmental conditions. The mass ratio between different sulfur sources influences the speed and the efficiency of the denitrification reaction, and the efficiency of the denitrification reaction can be enhanced through the proper mass ratio, so that nitrate and nitrite can be reduced into nitrogen more effectively, and the performance of the denitrifying bacteria culture complexing agent can be regulated.
In a preferred embodiment of the present invention, the iron source mixture of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage includes manganese iron ore powder, ferrous hydroxide and magnetic iron oxide; the iron source mixture comprises the following components in percentage by mass: ferrous hydroxide: magnetic iron oxide= (20-30): (0.5-3): (0.5-6). The technical effects are as follows: ensures that iron compounds with different forms exist in the iron source mixture, provides diversity and is helpful for adapting to denitrification reactions under different environmental conditions. The mass ratio between different iron sources influences the speed and the efficiency of the denitrification reaction, and the efficiency of the denitrification reaction can be enhanced by accurately adjusting the proper mass ratio, so that nitrate and nitrite can be reduced into nitrogen more effectively, and the performance of the denitrifying bacteria culture complexing agent can be regulated.
In a preferred embodiment of the present invention, the stabilizer of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage includes calcium chloride and magnesium oxide; the stabilizer comprises the following components in percentage by mass: magnesium oxide= (1-5): (0.3-3). The technical effects are as follows: calcium chloride and magnesium oxide are relatively safe compounds, and small additions do not adversely affect the rancour wastewater treatment process. The pH value of the denitrifying bacteria culture complexing agent is adjusted through the synergistic effect of the calcium chloride and the magnesium oxide, so that the excessive fluctuation of the pH value is prevented, proper conditions are provided for the growth and the activity of bacteria, and the growth of the bacteria and the stability of the denitrification reaction are ensured. Meanwhile, calcium chloride and magnesium oxide are important components of cell synthesis and enzyme activity, and can be used as sources of calcium and magnesium through proper mass ratio to promote the growth and activity of denitrifying bacteria.
In a preferred embodiment of the present invention, the composite adhesive of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage includes phosphate, water-soluble natural resin and modifier; the composite adhesive comprises the following components in percentage by mass: water-soluble natural resin: modifier= (20-35): (65-80): (2-10). The technical effects are as follows: phosphate, water-soluble natural resin and modifier in the composite adhesive are taken as carriers of denitrifying bacteria to jointly form a basic structure of the composite adhesive, a proper growth and attachment surface is provided for bacteria, and meanwhile, the composite adhesive has adhesiveness and chemical stability through a proper proportion, so that the requirements of denitrifying bacteria culture are fully met.
In a preferred embodiment of the present invention, the modifier of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage includes silica nanoparticles, activated carbon, sodium dodecyl sulfate, polyvinyl alcohol and dimethyl ethylene diamine; the mass ratio of each component in the modifier is that silicon oxide nano particles: activated carbon: sodium dodecyl sulfate: polyvinyl alcohol: dimethylethylenediamine= (1-5): (1-3): (1-3): (0.5-2): (0.5-1). The technical effects are as follows: sodium dodecyl sulfate is used as a surfactant and can be used for improving the dispersibility of the composite adhesive; the polyvinyl alcohol is a modified polymer, so that the viscosity and the adhesiveness of the composite adhesive can be adjusted; the dimethyl ethylene diamine is used as a cross-linking agent, so that the stability and durability of the composite adhesive can be improved. By selecting proper modifier and improving the proportion, the adsorption performance and the surface activity of the composite adhesive are enhanced, and the attachment and the reaction of nitrifying bacteria on a substrate are promoted. The interaction of different components in the modifier improves the stability of the composite adhesive. The property and the characteristic of the composite adhesive are adjusted by precisely controlling the proportion, so that the culture requirement of specific denitrifying bacteria is met. So that the compound adhesive can be used as a carrier and can provide advantages in chemical properties such as reaction capability in the culture process of denitrifying bacteria.
Referring to fig. 2, the invention provides a preparation method of a denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, wherein the denitrifying bacteria culture complexing agent is prepared from a sulfur source mixture, an iron source mixture, a stabilizer and a compound adhesive, and the components and the mass percentages of the components are as described above, and the preparation method comprises the following steps: s100, taking all the components according to mass percentages; s200, adding the components into a container, mixing, grinding and uniformly stirring to obtain a mixture; and S300, heating the mixture, calcining and forming at a high temperature of 160-180 ℃, and cooling at normal temperature to obtain a denitrifying bacteria culture complexing agent finished product.
Referring to fig. 3, the invention provides an application of a denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, wherein the denitrifying bacteria culture complexing agent is prepared from a sulfur source mixture, an iron source mixture, a stabilizer and a compound adhesive, and the components and the mass percentages of the components are as described above, and the application steps comprise: s1000, inoculating sludge into the prepared denitrifying bacteria culture complexing agent to obtain bacterial nests; s2000, cleaning the bacterial nest with distilled water, removing impurities, and centrifuging at 80rpm/S to obtain denitrifying bacteria filler; s3000, sequentially filling cobbles, denitrifying bacteria fillers and sewage to be degraded from bottom to top in the sewage degradation reactor, introducing distilled water into the sewage degradation reactor through the adjustment of a water inlet valve, and controlling the aeration rate in the sewage degradation reactor through an oxygenation pump.
In a preferred embodiment of the present invention, in the application of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, the denitrifying bacteria in the bacterial nest include at least one of sulfur autotrophic denitrifying bacteria (thiobacillus denitrificans), pseudomonas pastoris (paracoccus pantotrophus), sulfamonas (sulfarimonas), iron autotrophic denitrifying bacteria (acidithiobacillus ferrooxidans) and iron sulfide (thiobacillus ferrooxidans). The technical effects are as follows: through directional culture, the bacterial nest contains different types of denitrifying bacteria, such as sulfur autotrophic denitrifying bacteria, pseudomonas pastoris, sulfate monad, iron autotrophic denitrifying bacteria, sulfur ferric monad and the like, and the diversity is favorable for meeting nitrogen removal requirements under different water quality conditions, so that the adaptability and the stability of the treatment system are improved.
In a preferred embodiment of the present invention, in the application of the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, a carbon source is added between the denitrifying bacteria filler and sewage to be degraded in the sewage degradation reactor, the carbon source includes shell powder, and the mass ratio of the denitrifying bacteria filler to the shell powder is that of the denitrifying bacteria filler: shell powder = 1:5, the preparation method of the shell powder comprises the following steps: and (3) taking shells, cleaning the shells with distilled water, removing impurities, cleaning the shells with dilute hydrochloric acid, drying, and grinding to obtain shell powder. The technical effects are as follows: the shell powder is added as a carbon source to provide additional organic carbon for denitrifying bacteria, which is helpful for promoting the growth and metabolism of bacteria. The mass ratio of denitrifying bacteria filler to shell powder is 1: and 5, adjusting the carbon-nitrogen ratio to ensure that the provided carbon source and nitrogen compounds in the sewage have proper proportions, thereby being beneficial to optimizing the denitrification reaction efficiency and improving the nitrogen removal performance.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, the content of each component is expressed in terms of mass percent, and the specific mass is not limited, and the mass percent ratio is satisfied.
(one) example 1: the mass percentages of the components of the denitrifying bacteria culture complexing agent are shown in table 1.
Table 1: example 1 mass percent of each component in denitrifying bacteria culture complex
Sulfuric acid 25%
Sodium sulfide 16%
Sodium thiosulfate 15%
Manganite powder 20%
Ferrous hydroxide 5%
Magnetic iron oxide 3%
Calcium chloride 5%
Magnesium oxide 1%
Phosphate salts 2%
Water-soluble natural resin 7%
Silicon oxide nanoparticles 0.2%
Activated carbon 0.1%
Sodium dodecyl sulfate 0.15%
Polyvinyl alcohol 0.25%
Dimethyl ethylene diamine 0.3%
The preparation method comprises the following steps:
taking the components according to the mass percentages in the table 1;
adding the components into a container, mixing, grinding and uniformly stirring to obtain a mixture;
and heating the mixture, calcining at a high temperature of 180 ℃ for molding, and cooling at normal temperature to obtain a denitrifying bacteria culture complexing agent finished product.
(II) example 2: the mass percentages of the components of the denitrifying bacteria culture complexing agent are shown in table 2.
Table 2: example 2 mass percent of each component in denitrifying bacteria culture complex
Sulfuric acid 22%
Sodium sulfide 12%
Sodium thiosulfate 13%
Manganite powder 14%
Ferrous hydroxide 10%
Magnetic iron oxide 11%
Calcium chloride 6%
Magnesium oxide 2%
Phosphate salts 2%
Water-soluble natural resin 6.5%
Silicon oxide nanoparticles 1%
Activated carbon 0.9%
Sodium dodecyl sulfate 0.8%
Polyvinyl alcohol 0.4%
Dimethyl ethylene diamine 0.4%
The preparation method comprises the following steps:
taking the components according to the mass percentages in the table 2;
adding the components into a container, mixing, grinding and uniformly stirring to obtain a mixture;
and heating the mixture, calcining at a high temperature of 180 ℃ for molding, and cooling at normal temperature to obtain a denitrifying bacteria culture complexing agent finished product.
(III) example 3: the mass percentages of the components of the denitrifying bacteria culture complexing agent are shown in table 3.
Table 3: example 3 mass percent of each component in denitrifying bacteria culture complex
Sulfuric acid 28%
Sodium sulfide 16%
Sodium thiosulfate 16%
Manganite powder 12%
Ferrous hydroxide 8%
Magnetic iron oxide 5%
Calcium chloride 4%
Magnesium oxide 3%
Phosphate salts 3%
Water-soluble natural resin 4%
Silicon oxide nanoparticles 0.3%
Activated carbon 0.3%
Sodium dodecyl sulfate 0.2%
Polyvinyl alcohol 0.15%
Dimethyl ethylene diamine 0.05%
The preparation method comprises the following steps:
taking the components according to the mass percentages in the table 3;
adding the components into a container, mixing, grinding and uniformly stirring to obtain a mixture;
and heating the mixture, calcining at a high temperature of 180 ℃ for molding, and cooling at normal temperature to obtain a denitrifying bacteria culture complexing agent finished product.
(IV) example 4: the mass percentages of the components of the denitrifying bacteria culture complexing agent are shown in table 4.
Table 4: example 4 mass percent of each component in denitrifying bacteria culture complex
Sulfuric acid 5%
Sodium sulfide 10%
Sodium thiosulfate 13%
Manganite powder 26%
Ferrous hydroxide 18%
Magnetic iron oxide 12%
Calcium chloride 5%
Magnesium oxide 1%
Phosphate salts 2%
Water-soluble natural resin 7%
Silicon oxide nanoparticles 0.2%
Activated carbon 0.1%
Sodium dodecyl sulfate 0.15%
Polyvinyl alcohol 0.25%
Dimethyl ethylene diamine 0.3%
The preparation method comprises the following steps:
the components are taken according to the mass percentages in the table 4;
adding the components into a container, mixing, grinding and uniformly stirring to obtain a mixture;
and heating the mixture, calcining at 160 ℃ at high temperature for molding, and cooling at normal temperature to obtain a denitrifying bacteria culture complexing agent finished product.
(fifth) example 5: the mass percentages of the components of the denitrifying bacteria culture complexing agent are shown in table 5.
Table 5: example 5 mass percent of each component in denitrifying bacteria culture complex
Sulfuric acid 25%
Sodium sulfide 16%
Sodium thiosulfate 15%
Manganite powder 20%
Ferrous hydroxide 5%
Magnetic iron oxide 3%
Calcium chloride 3%
Magnesium oxide 3%
Phosphate salts 3%
Water-soluble natural resin 6%
Silicon oxide nanoparticles 0.2%
Activated carbon 0.1%
Sodium dodecyl sulfate 0.15%
Polyvinyl alcohol 0.25%
Dimethyl ethylene diamine 0.3%
The preparation method comprises the following steps:
the components are taken according to the mass percentages in the table 5;
adding the components into a container, mixing, grinding and uniformly stirring to obtain a mixture;
and heating the mixture, calcining at 160 ℃ at high temperature for molding, and cooling at normal temperature to obtain a denitrifying bacteria culture complexing agent finished product.
Sixth example 6: the mass percentages of the components of the denitrifying bacteria culture complexing agent are shown in table 6.
Table 6: example 6 mass percent of each component in denitrifying bacteria culture complex
Sulfuric acid 25%
Sodium sulfide 16%
Sodium thiosulfate 15%
Manganite powder 20%
Ferrous hydroxide 5%
Magnetic iron oxide 3%
Calcium chloride 5%
Magnesium oxide 1%
Phosphate salts 3%
Water-soluble natural resin 5%
Silicon oxide nanoparticles 0.5%
Activated carbon 0.2%
Sodium dodecyl sulfate 0.3%
Polyvinyl alcohol 0.8%
Dimethyl ethylene diamine 0.2%
The preparation method comprises the following steps:
taking the components according to the mass percentages in the table 6;
adding the components into a container, mixing, grinding and uniformly stirring to obtain a mixture;
and heating the mixture, calcining at a high temperature of 170 ℃ for molding, and cooling at normal temperature to obtain a denitrifying bacteria culture complexing agent finished product.
(seventh) example 7: the mass percentages of the components of the denitrifying bacteria culture complexing agent are shown in table 7.
Table 7: example 7 mass percent of each component in denitrifying bacteria culture complex
Sulfuric acid 5%
Sodium sulfide 10%
Sodium thiosulfate 13%
Manganite powder 26%
Ferrous hydroxide 18%
Magnetic iron oxide 12%
Calcium chloride 5%
Magnesium oxide 1%
Phosphate salts 3%
Water-soluble natural resin 5%
Silicon oxide nanoparticles 0.5%
Activated carbon 0.2%
Sodium dodecyl sulfate 0.3%
Polyvinyl alcohol 0.8%
DimethylethyleneDiamines 0.2%
The preparation method comprises the following steps:
taking the components according to the mass percentages in the table 7;
adding the components into a container, mixing, grinding and uniformly stirring to obtain a mixture;
and heating the mixture, calcining at a high temperature of 170 ℃ for molding, and cooling at normal temperature to obtain a denitrifying bacteria culture complexing agent finished product.
(eighth) example 8: the mass percentages of the components of the denitrifying bacteria culture complexing agent are shown in table 8.
Table 8: example 8 mass percent of each component in denitrifying bacteria culture complex
Sulfuric acid 18%
Sodium sulfide 16%
Sodium thiosulfate 22%
Manganite powder 20%
Ferrous hydroxide 5%
Magnetic iron oxide 3%
Calcium chloride 5%
Magnesium oxide 1%
Phosphate salts 2%
Water-soluble natural resin 7%
Silicon oxide nanoparticles 0.2%
Activated carbon 0.1%
Sodium dodecyl sulfate 0.15%
Polyvinyl alcohol 0.25%
Dimethyl ethylene diamine 0.3%
The preparation method comprises the following steps:
the components are taken according to the mass percentages in the table 8;
adding the components into a container, mixing, grinding and uniformly stirring to obtain a mixture;
and heating the mixture, calcining at 160 ℃ at high temperature for molding, and cooling at normal temperature to obtain a denitrifying bacteria culture complexing agent finished product.
(ninth) example 9: the mass percentages of the components of the denitrifying bacteria culture complexing agent are shown in table 9.
Table 9: example 9 mass percent of each component in denitrifying bacteria culture complex
Sulfuric acid 25%
Sodium sulfide 16%
Sodium thiosulfate 15%
Manganite powder 10%
Ferrous hydroxide 8%
Magnetic iron oxide 10%
Calcium chloride 5%
Magnesium oxide 1%
Phosphate salts 2%
Water-soluble natural resin 7%
Silicon oxide nanoparticles 0.2%
Activated carbon 0.1%
Sodium dodecyl sulfate 0.15%
Polyvinyl alcohol 0.25%
Dimethyl ethylene diamine 0.3%
The preparation method comprises the following steps:
the components are taken according to the mass percentages in the table 9;
adding the components into a container, mixing, grinding and uniformly stirring to obtain a mixture;
and heating the mixture, calcining at a high temperature of 180 ℃ for molding, and cooling at normal temperature to obtain a denitrifying bacteria culture complexing agent finished product.
(ten) Performance test
Sampling sewage in a certain flood discharge river channel water body, and degrading sludge in a sewage reactor device to adopt a certain section of black and odorous water body of the river channel.
The sewage degradation reactor is shown in figure 3 and comprises a water inlet tank 1, a water inlet valve 2, a water inlet rotameter 3, a small bacterial nest generator 4, an aeration rotameter 5 and an oxygenation pump 6. The water inlet valve 2 is opened, the rotating speed is checked through the water inlet rotameter 3, the constant water inlet of the control system is realized, the sewage enters the small bacterial nest generator 4 from the water inlet water tank 1 for treatment, and the aeration quantity of the oxygenation pump 6 is controlled according to the specific implementation requirement. The sewage degrading reactor is one kind of high efficiency water purifying equipment developed through combining small bacteria nest technology and aeration and oxygenation technology, and has the core part of small bacteria nest generator, flow making and aeration equipment. The small bacterial nest generator 4 consists of a box body and small bacterial nests, and DO in the water body is increased through microporous aeration of the flow-making aeration equipment, so that enough oxygen can be provided for survival and propagation of microorganisms.
Total Nitrogen (TN), ammonia Nitrogen (NH) 4 + -N), nitrate nitrogen (NO 3 -N), nitrite nitrogen (NO 2 -N) is measured by referring to a standard method, ammonia nitrogen is measured by adopting a Nahner reagent spectrophotometry, nitrate nitrogen is measured by adopting an ultraviolet spectrophotometry, nitrite nitrogen is measured by adopting an N- (1-naphthyl) -ethylenediamine spectrophotometry, and total nitrogen is measured by adopting an alkaline potassium persulfate digestion ultraviolet spectrophotometry.
Table 10 total nitrogen concentration and removal rate in performance test
Treatment mode Total nitrogen concentration mg/L Total nitrogen removal rate Ammonia nitrogen removal rate Nitrate nitrogen removal rate Nitrite nitrogen removal rate
Blank group 60 0 0 0 0
Example 1 2 97.5% 96% 96.8% 98.5%
Example 2 5 91.7% 92.6% 91.5% 93.2%
Example 3 2 93.5% 93.8% 92.5% 92.8%
Example 4 3 92.8% 92.2% 92.6% 93.5%
Example 5 2.5 91.5% 92% 92.3% 91.7%
Example 6 2 95.8% 93.6% 94.5% 94.3%
Example 7 3 92.7% 94.2% 94.6% 93.7%
Example 8 3.5 94.6% 93.9% 95.7% 94.9%
Example 9 2 96.4% 95.3% 94.8% 95.9%
Three equal-volume water tanks (900L) are prepared, and the three water tanks are divided into a group, b group and c group according to the feeding proportion of the small bacteria nest of 40%, 60% and 80%. Five gradient runs were set up per group at total nitrogen concentrations of 10 (mg/L), 30 (mg/L), 50 (mg/L), 75 (mg/L), 100 (mg/L). The time taken for the total nitrogen removal rate to reach 80% was counted (sampling was performed every 0.5h, and total nitrogen, ammonia nitrogen, nitrate, nitrite content were detected, respectively) as shown in table 11.
Table 11 time required to remove 80% of total nitrogen in performance test
TN content feed ratio 1-10(mg/L) 10-30(mg/L) 30-50(mg/L) 50-75(mg/L) 75-100(mg/L)
40% 2h 6.8h 12h 18h 24h
60% 1h 3.4h 6h 9h 12h
80% 0.5h 1.7h 3h 4.5h 6h
In the performance test, various physical and chemical indexes are detected by adopting a national standard method.
As can be seen from the table, in the denitrifying bacteria culture complexing agent for degrading nitrogen in sewage prepared by the invention, the ratio of the sulfur source mixture to the iron source mixture is an important factor influencing the denitrification efficiency, and the result shows that when the mass percentage of the sulfur source mixture is 56%, the mass percentage of the iron source mixture is 28%, namely the ratio is 2:1, the denitrification effect is best, and the total nitrogen removal rate can reach 97.5% after three days of operation.
When the stabilizer is not added or the proportion of the stabilizer is not the optimal proportion, the ammonia nitrogen concentration of the effluent is too high to reach the effluent standard, because the denitrification is an acidogenic reaction, SO is generated 4 2- When the nitrogen removal amount is high, SO 4 2- The yield of the water is also high, and a good water outlet effect cannot be achieved. By adding a proper amount of stabilizer, the method provides proper environmental conditions for the growth of denitrifying bacteria, and reduces SO while the nitrogen removal amount is higher 4 2- The content of (3) ensures that the removing effect is more stable.
The denitrification effect of the denitrifying bacteria filler is best, wherein 56% of sulfur source mixture and 28% of iron source mixture are used as nutrients, 6% of stabilizer and 10% of composite adhesive, wherein the stabilizer comprises 5% of calcium chloride, 1% of magnesium oxide, 2% of phosphate in the composite adhesive, 7% of water-soluble natural resin, 0.2% of silicon oxide nano particles, 0.1% of activated carbon, 0.15% of sodium dodecyl sulfate, 0.25% of polyvinyl alcohol and 0.3% of dimethyl ethylene diamine. Wherein the stabilizer can help to maintain the pH stability of the culture medium, provide proper environmental conditions for the growth of denitrifying bacteria, improve the growth performance of denitrifying bacteria, and increase the yield of denitrifying bacteria; the compound adhesive has a promoting effect on improving the microbial activity, increases the contact between denitrifying bacteria and the culture solution, improves the degradation efficiency of nitrogen compounds, provides a certain protection, helps the denitrifying bacteria resist external adverse conditions, and maintains the stability of the denitrifying bacteria culture.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.

Claims (10)

1. The denitrifying bacteria culture complexing agent for degrading nitrogen in sewage is characterized by comprising the following components in percentage by mass:
35% -60% of a sulfur source mixture, wherein the sulfur source mixture comprises a compound containing sulfur elements;
15% -60% of an iron source mixture, wherein the iron source mixture comprises a compound containing iron elements;
3% -8% of a stabilizer, wherein the stabilizer regulates the PH value of the denitrifying bacteria culture complexing agent;
3-10% of composite adhesive, wherein the composite adhesive is a carrier of denitrifying bacteria.
2. The denitrifying bacteria culture complex for degrading nitrogen in sewage according to claim 1, wherein,
the sulfur source mixture comprises sulfuric acid, sodium sulfide and sodium thiosulfate;
the sulfur source mixture comprises the following components in percentage by mass: sodium sulfide: sodium thiosulfate= (20-30): (15-25): (15-25).
3. The denitrifying bacteria culture complex for degrading nitrogen in sewage according to claim 1, wherein,
the iron source mixture includes ferrimanganite fines, ferrous hydroxide and magnetic iron oxide;
the iron source mixture comprises the following components in percentage by mass: ferrous hydroxide: magnetic iron oxide= (20-30): (0.5-3): (0.5-6).
4. The denitrifying bacteria culture complex for degrading nitrogen in sewage according to claim 1, wherein,
the stabilizer comprises calcium chloride and magnesium oxide;
the stabilizer comprises the following components in percentage by mass: magnesium oxide= (1-5): (0.3-3).
5. The denitrifying bacteria culture complex for degrading nitrogen in sewage according to claim 1, wherein,
the composite adhesive comprises phosphate, water-soluble natural resin and a modifier;
the composite adhesive comprises the following components in percentage by mass: water-soluble natural resin: modifier= (20-35): (65-80): (2-10).
6. The denitrifying bacteria culture complex for degrading nitrogen in sewage according to claim 5, wherein,
the modifier comprises silicon oxide nano particles, active carbon, sodium dodecyl sulfate, polyvinyl alcohol and dimethyl ethylene diamine;
the mass ratio of each component in the modifier is that silicon oxide nano particles: activated carbon: sodium dodecyl sulfate: polyvinyl alcohol: dimethylethylenediamine= (1-5): (1-3): (1-3): (0.5-2): (0.5-1).
7. A method for preparing a denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, which is characterized in that the denitrifying bacteria culture complexing agent is prepared from a sulfur source mixture, an iron source mixture, a stabilizer and a compound adhesive, wherein the components comprise the components and the mass percentages of the components are as set forth in any one of claims 1-6, and the preparation steps comprise:
s100, taking all the components according to mass percentages;
s200, adding the components into a container, mixing, grinding and uniformly stirring to obtain a mixture;
and S300, heating the mixture, calcining and forming at a high temperature of 160-180 ℃, and cooling at normal temperature to obtain a denitrifying bacteria culture complexing agent finished product.
8. The application of a denitrifying bacteria culture complexing agent for degrading nitrogen in sewage, which is characterized by comprising a sulfur source mixture, an iron source mixture, a stabilizer and a compound adhesive, wherein the denitrifying bacteria culture complexing agent comprises the following components in percentage by mass as claimed in any one of claims 1 to 6, and the application steps comprise:
s1000, inoculating sludge into the prepared denitrifying bacteria culture complexing agent to obtain bacterial nests;
s2000, cleaning the bacterial nest with distilled water, removing impurities, and centrifuging at 80rpm/S to obtain denitrifying bacteria filler;
s3000, sequentially filling cobbles, denitrifying bacteria fillers and sewage to be degraded from bottom to top in the sewage degradation reactor, introducing distilled water into the sewage degradation reactor through the adjustment of a water inlet valve, and controlling the aeration rate in the sewage degradation reactor through an oxygenation pump.
9. The use of the denitrifying bacteria culture complex agent for degrading nitrogen in sewage according to claim 8, characterized in that,
the denitrifying bacteria in the bacterial nest comprise at least one of sulfur autotrophic denitrifying bacteria, pseudomonas pastoris, sulfate monad, iron autotrophic denitrifying bacteria and sulfur ferric monad.
10. The use of a denitrifying bacteria culture complexing agent for degrading nitrogen in sewage according to claim 8, further comprising adding a carbon source between the denitrifying bacteria filler and the sewage to be degraded in the degradation sewage reactor, wherein the carbon source comprises shell powder, and the mass ratio of the denitrifying bacteria filler to the shell powder is that of the denitrifying bacteria filler: shell powder = 1:5, the preparation method of the shell powder comprises the following steps:
and (3) taking shells, cleaning the shells with distilled water, removing impurities, cleaning the shells with dilute hydrochloric acid, drying, and grinding to obtain shell powder.
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